Calculation of the magnetic hyperfine structure in the ground electronic state of HCCO

Abstract

In this paper we analyze the spin-spin hyperfine interaction in the two components of the ground electronic state of the free π radical HCCO, A2A′[2Π] and X2A″. Electronic mean values of the Fermi contact constants of all magnetic nuclei [1H, 13C1, 13C2,17O] are calculated using models that include the electron-correlation correction, primarily CCSD method in the cc-pwCVTZ basis set and B3LYP functional in the cc-pCVQZ basis set. Also, we have calculated components of the anisotropic hyperfine tensor for the ground X2A″ state. The dependence of hyperfine coupling constants (HFCCs) on the two bending coordinates is examined, and the results of HCC bending (vibrational) averaging of electronic mean values are presented for both states. It is demonstrated that electronic and subsequent vibrational averaging of the HFCCs suffices for obtaining results that are in good agreement with available experimental findings (for proton) in the X2A″ state, owing to a small geometry dependence of these quantities, and relatively distant minimum from linearity. © 2007 Elsevier Inc. All rights reserved.